A Reinvestigation by Circular Dichroism and NMR: Ruthenium(II) and Rhodium(III) Metallointercalators Do Not Bind Cooperatively to DNA

Fast, long-range electron transfer mediated by the DNA helix has been questioned by some researchers citing the possible clustering, or cooperative association, of noncovalently bound donors and acceptors on DNA. A systematic investigation of binding to DNA by the metallointercalators Δ-bis(1,10-phenanthroline)(dipyridophenazine)ruthenium(II) (Ru), Δ-bis(9,10-phenanthrenequinone diimine)(2,2‘-bipyridine)rhodium(III) (Rh), and Δ-bis(9, 10-phenanthrenequinone diimine)(5-(amidoglutaryl)-1,10-phenanthroline)rhodium(III) (Rh‘) using circular dichroism and NMR has shown no evidence for their cooperative clustering on a DNA helix. Circular dichroism (CD) studies of Ru and Rh in [poly(dA-dT)]2, mixed-sequence calf thymus DNA, and [poly(dG-dC)]2 as a function of loading indicate that the largest perturbations to the CD signal occur upon initial addition of DNA, with no subsequent systematic variation. Difference spectra of the two metallointercalators bound together versus separately are virtually indistinguishabl...